CN102219671A - Method for selective hydrogenation of aromatic aldehydes for refining terephthalic acid - Google Patents
Method for selective hydrogenation of aromatic aldehydes for refining terephthalic acid Download PDFInfo
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- CN102219671A CN102219671A CN2010101471598A CN201010147159A CN102219671A CN 102219671 A CN102219671 A CN 102219671A CN 2010101471598 A CN2010101471598 A CN 2010101471598A CN 201010147159 A CN201010147159 A CN 201010147159A CN 102219671 A CN102219671 A CN 102219671A
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- terephthalic acid
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Abstract
The invention relates to a method for the selective hydrogenation of aromatic aldehydes for refining terephthalic acid, which mainly solves the problems that p-toluic acid (referred to as P-TA) is mainly generated by the hydrogenation of 4-carboxy-benzaldehyde (referred to as 4-CBA), and the generated 4-(hydroxymethyl)benzoic acid (referred to as 4-HMBA) is low in both selectivity and yield in the prior art. According to the invention, the problems are well solved by adopting the technical scheme that operations are carried out at the reaction temperature from 265 to 285 DEG C, the reaction pressure from 7.2 to 8.5MPa and the hydrogen partial pressure from 0.6 to 1.2MPa by using carbon nanofiber (referred to as CNF) as a carrier and using loaded palladium and at least one of the metals, such as ruthenium, nickel, zinc, copper or iron or oxides thereof as a catalyst, and the method can be used in the industrial production of hydrogenated refinement of the terephthalic acid.
Description
Technical field
The present invention relates to a kind of method of hydrotreating that is used for purification of terephthalic acid, be particularly related to the method for the aromatic aldehyde selective hydrogenation of the treating process that is used for terephthalic acid, wherein to the high generation of selecting of carboxyl benzaldehyde (be called for short 4-CBA) selective hydrogenation to hydroxymethyl-benzoic acid (being called for short 4-HMBA).
Background technology
The loading type Pd/carbon catalyst is applicable to the refining of crude terephthalic acid, in the crude terephthalic acid carboxyl benzaldehyde impurity such as (being called for short 4-CBA) is carried out adopting the crystalline method to separate purification subsequently after hydrogenation changes other compound into.In industrial production, the 4-CBA hydrogenation in the crude terephthalic acid mainly generates p-methylbenzoic acid (P-TA), and contains the 4-HMBA of minute quantity.
4-HMBA is used for synthetic corresponding homopolymer, poly-para Toluic Acid's salt or corresponding ester as a kind of important monomer, and poly-methyl is to hydroxymethyl-benzoic acid ester (mep-HMB).Because 4-HMBA more is soluble in than PT acid and is easy in the aqueous solvent separate with PTA, and each carbonyl hydrogen becomes alcohol only to need to consume the active hydrogen of 1 molecule.And hydrogenolysis becomes hydrocarbon, and then the hydrogen consumption doubles.If, will help reducing lock out operation expense and energy consumption so can realize that 4-CBA selects to be hydrogenated to 4-HMBA, existing hydrofining technology is greatly simplified, reduce cost of investment and running cost, improve the PTA competitiveness of product in market.
About the report of 4-HMBA seldom, among the patent US 4892972 of Amoco company application, mentioned the 4-CBA hydrogenation and can generate 4-HMBA, but, do not generated the 4-HMBA reaction at the 4-CBA hydrogenation specially and study report just as the hydrorefined attached reaction of a kind of 4-CBA.On Pd/C and Rh/C catalyzer, at 277 ℃, 0.34MPa, in reactor, the amount of 4-HMBA increases earlier with the prolongation in reaction times, and reduce the back.React 4h at the end, the 4-HMBA amount was more than 0.5%Rh/C when 0.5%Pd/C made catalyzer, but all was lower than the amount of PT acid in the whole process.In the patent US 5387726 of Degussa company application, selective hydrogenation compares detailed research to 4-CBA.The 4-CBA aqueous solution with 1% is reactant, with Pd/TiO
2(pure anatase octahedrite) is catalyzer, and at 150 ℃, 1MPa, 4-CBA transformation efficiency are 89%, and the selectivity of 4-HMBA is higher than 95%.But when temperature of reaction rises to 250 ℃ by 150 ℃, then generate the ring hydrogenation products 4-methyl cyclohexane acid more than 70%.In the patent CN94100192.X of Degussa company application, under the hydrorefined industrial condition of terephthalic acid, adopt Pd/TiO
2Catalyzer reacted 4 hours, and the 4-CBA transformation efficiency is greater than 90%, and the selectivity of 4-HMBA reaches 48.3%.In the patent US 6706658 of Englehard company application, the charcoal of extruding with different pore size distributions is made carrier, the Pd/C catalyzer that load P d makes carries out purification of terephthalic acid, the ratio of HMBA/PT acid is up to 3.25 in the product, the catalyst stability height, deactivation rate is low, but does not have the relevant report of catalyst activity.
Carbon nano fiber has bigger superiority as a kind of novel carriers material than traditional absorbent charcoal carrier, and its particular structure makes catalyzer have special activity and selectivity.The diameter of carbon nano fiber is generally about tens nanometers, and with clipped wire submanifold sizableness, so metallics can well disperse on carbon nano fiber, and is evenly distributed; The pore size distribution of carbon nano fiber is more even, based on mesopore, helps passing through of reactant and product, thereby improves selectivity of catalyst; The carbon nano fiber particular structure makes it have very strong interfacial effect, makes metallics and carrier-bound more firm, has delayed the loss of active ingredient in reaction.The patent CN200510024520 of East China University of Science's application is a carrier with board-like carbon fiber, is active ingredient with the palladium, the hydrorefined performance of catalyzer terephthalic acid of investigation, and the transformation efficiency of 4-CBA is below 98%.The inventor found through experiments, and is carrier by adopting carbon fiber, and under the hydrogenation activity that guarantees 4-CBA, its selectivity that is converted into 4-HMBA reaches 60%.
Summary of the invention
Technical problem to be solved by this invention be exist in the conventional art carboxyl benzaldehyde (be called for short 4-CBA) hydrogenation is mainly generated p-methylbenzoic acid (being called for short P-TA), the selectivity that generates 4-HMBA is low, the problem that yield is low provides a kind of new aromatic aldehyde selective hydrogenation method that is used for purification of terephthalic acid.This method is used for the hydrofining reaction of crude terephthalic acid with this catalyzer, have under the reaction conditions of High Temperature High Pressure, in highly acid reaction medium, under the prerequisite that guarantees the higher hydrogenation activity of catalyzer, have the high characteristics of selectivity height, yield that the 4-CBA reduction generates 4-HMBA.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method that is used for the aromatic aldehyde selective hydrogenation of purification of terephthalic acid, in temperature of reaction is that 265～285 ℃, reaction pressure are 7.2～8.0MPa, the hydrogen dividing potential drop is under the condition of 0.5～1.5MPa, the terephthaldehyde's acid starting material that contains carboxyl benzaldehyde contacts with catalyzer, the reaction to carboxyl benzaldehyde in the raw material is generated hydroxymethyl-benzoic acid, and wherein used catalyzer comprises following component by weight percentage:
A) 0.05～1% palladium or its oxide compound;
B) 0.01～5% be selected from least a metal or its oxide compound in ruthenium, nickel, zinc, copper or the iron;
C) 94.0～99.8% carbon fibre carrier.
In the technique scheme, the temperature of reaction preferable range is 270～280 ℃, and the reaction pressure preferable range is 7.5～8.0MPa, and hydrogen dividing potential drop preferable range is 0.8～1.0MPa; The consumption weight percent preferable range of palladium or its oxide compound is 0.1～0.8%, and more preferably scope is 0.2～0.5%; The preferable range that is selected from least a metal of ruthenium, nickel, zinc, copper or iron or its oxide compound is 0.2～5%, and more preferably scope is 0.3～5%; The preferable range of carbon fibre carrier consumption is 95～99.8%.
The raw material that active constituent of the present invention is suitable for is as follows:
Palladium: with its muriate, oxide compound, acetate, nitrate, the acid of chlorine palladium and subsalt thereof, palladium amine complex;
Ruthenium: with its muriate, oxide compound;
Nickel, zinc, copper, iron: with its oxide compound, muriate, acetate, nitrate or other soluble salt.
Preparation of catalysts method of the present invention is as follows:
1. the preparation of carbon nano fiber: take by weighing 2～4g levigated iron nitrate or nickelous nitrate powder, place quartz boat, and make its homodisperse, and quartz boat is put into quartz tube reactor, be warming up to 600 ℃ then, feed argon gas (600ml/min) and hydrogen (400ml/min) simultaneously, and, switch gas then at 600 ℃ of constant temperature reduction 4～8h, feed carbon monoxide (800ml/min) and hydrogen (200ml/min), finish cool to room temperature under the argon shield behind reaction 16～20h; With the carbon fiber of preparation with nitric acid dousing 8～12h of 5～10%, with the pure water washing to neutrality; Standby at 110～130 ℃ of drying 4～8h then.Specific surface with BET method test sample is 250～300m
2/ g, total pore volume is 0.52～0.58cm
3/ g.
2. active constituent aqueous solution adding tensio-active agent and yellow soda ash are mixed with catalyst activity component solution, adopt methods such as dipping or sprinkling to make the active constituent metal load then, preferred pickling process in carrier carbon nano fiber surface.0～50 ℃ of dipping temperature is generally room temperature.
3. catalyzer in air aging 1～24 hour then adopts reductive agent to reduce processing.Reductive agent can adopt formic acid, sodium formiate, formaldehyde, hydrazine hydrate, glucose and hydrogen, preferred hydrogen.100～500 ℃ of reduction temperatures, preferred 100～250 ℃.0.5～10 hour recovery time, preferred 1～4 hour.
Among the present invention owing in Pd/ carbon fiber catalyzer, added ruthenium, nickel, zinc, copper or iron isoreactivity component, make catalyzer under the harsh reaction conditions of refining crude terephthalic acid, remove impurity 4-CBA high conversion, and its highly selective is converted into 4-HMBA, both satisfied the requirement of crude terephthalic acid purified, to help again reducing process cost and energy consumption, existing hydrofining technology is greatly simplified, reduce cost of investment and running cost.Catalyzer of the present invention is used for the method for the hydrofining reaction of crude terephthalic acid, at 270～280 ℃, under the reaction conditions of 7.5～8.0MPa, the 4-CBA transformation efficiency is 99.3%, the selectivity of 4-HMBA is 62%, and the yield of 4-HMBA can reach 60%, has obtained better technical effect.
Activity rating of catalyst condition in autoclave:
Catalyst levels: 2.0 grams
Crude terephthalic acid amount: 30.0 grams
4-CBA amount: 1.0 grams
Sampling analysis adopts high pressure liquid chromatographic analysis.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
Take by weighing 50 gram carbon nano fibers (being called for short CNF), specific surface is 265m
2/ g, pore volume are 0.53ml/g.In the washing still, be that 8% nitric acid carries out pickling with concentration, 100 ℃ of wash temperatures, 1 hour pickling time, then with deionized water wash to neutrality.And it is stand-by at 120 ℃ times dry 5 hours.Take by weighing 0.5 and restrain the chlorine palladium acid solution that contains palladium 20%, again to wherein adding 4.0 gram NiCl
2.6H
2O adds an amount of tensio-active agent and yellow soda ash again, add at last amount that deionized water is diluted to solution just the submergence absorbent charcoal carrier be advisable.With the catalyst activity component solution impregnating carrier, wear out and use hydrogen reducing after 24 hours, obtain catalyst prod with pure water washing to neutral and drying then.Activity rating condition: reaction pressure: 7.5MPa, temperature of reaction: 280 ℃, hydrogen dividing potential drop 0.8MPa.
[embodiment 2]
Catalyst preparation process and examination condition wherein take by weighing the chlorine palladium acid solution that 0.68 gram contains palladium 20% with embodiment 1, and the nickel of adding is 4.5 gram Ni (NO
3)
26H
2O.
[embodiment 3]
Catalyst preparation process and examination condition are with embodiment 1, and the nickel of adding is 1.0 gram Ni (CH
3COO)
24H
2O.
[embodiment 4]
Catalyst preparation process and examination condition be with embodiment 1, wherein takes by weighing the chlorine palladium acid solution that 1 gram contains palladium 20%, adds 0.3 gram ruthenium content greater than 37.3% RuCl
3N H
2O.
[embodiment 5]
Catalyst preparation process and examination condition wherein add 1.8 gram Cu (NO with embodiment 1
3)
23H
2O.
[embodiment 6]
Catalyst preparation process and examination condition wherein add 2.5 gram Zn (CH with embodiment 1
3COO)
22H
2O.
[embodiment 7]
Catalyst preparation process and examination condition be with embodiment 1, and wherein 0.2 gram ruthenium content is greater than 37.3% RuCl
3N H
2O, 1.0 gram Cu (NO
3)
23H
2O.
[comparative example 1]
Catalyst preparation process and examination condition wherein do not add nickel with embodiment 1.
[comparative example 2]
Catalyst preparation process and examination condition wherein take by weighing the chlorine palladium acid solution that 1.25 grams contain palladium 20% with comparative example 1.
Concrete active constituent, active constituent parent, active constituent content that each embodiment and comparative example adopt see Table 1, and what the catalyzer that makes adopted that above-mentioned activity rating condition carries out activity rating the results are shown in Table 2.
Table 1
| Activity of such catalysts component, parent and weight percent thereof | |
| Embodiment 1 | PdCl 2(0.2％)-NiCl 2(2%)/surplus CNF |
| Embodiment 2 | PdCl 2(0.3％)-Ni(NO 3) 2(2%)/surplus CNF |
| Embodiment 3 | PdCl 2(0.2％)-Ni(CH 3COO) 2(0.5%)/surplus CNF |
| Embodiment 4 | PdCl 2(0.4％)-RuCl 3(0.3%)/surplus CNF |
| Embodiment 5 | PdCl 2(0.2％)-Cu(NO 3) 2(1%)/surplus CNF |
| Embodiment 6 | PdCl 2(0.2％)-Zn(CH 3COO) 2(1.5%)/surplus CNF |
| Embodiment 7 | PdCl 2(0.4％)-RuCl 3(0.2％)-Cu(NO 3) 2(0.6%)/surplus CNF |
| Comparative example 1 | PdCl 2(0.2％)/C |
| Comparative example 2 | PdCl 2(0.5％)/C |
Table 2
| The 4-CBA transformation efficiency, % | The 4-HMBA selectivity, % | The 4-HMBA yield, % | |
| Embodiment 1 | 99.1 | 61.6 | 59.8 |
| Embodiment 2 | 99.3 | 62.0 | 60.0 |
| Embodiment 3 | 99.1 | 61.5 | 60.1 |
| Embodiment 4 | 99.5 | 62.5 | 60.6 |
| Embodiment 5 | 99.6 | 61.8 | 59.9 |
| Embodiment 6 | 98.9 | 58.9 | 58.6 |
| Embodiment 7 | 99.8 | 62.8 | 61.0 |
| Comparative example 1 | 82.9 | 8.0 | 6.6 |
| Comparative example 2 | 99.9 | 0.1 | 9.99 |
[embodiment 8～12]
Adopt the catalyst weight content PdCl of embodiment 7 preparations
2(0.4%)-RuCl
3(0.2%)-Cu (NO
3)
2(0.6%)/and surplus CNF, investigate under the differential responses condition performance of catalyzer.Concrete as table 3.
Table 3
| Reaction conditions | 4-CBA transformation efficiency % | 4-HMBA transformation efficiency % | 4-HMBA yield % | |
| Embodiment 7 | Pressure: 7.5MPa temperature: 280 ℃ of hydrogen dividing potential drop: 0.8MPa | ?99.8 | 62.8 | 61.0 |
| Embodiment 8 | Pressure: 7.8MPa temperature: 278 ℃ of hydrogen dividing potential drop: 0.8MPa | ?99.6 | 62.5 | 60.8 |
| Embodiment 9 | Pressure: 8.0MPa temperature: 278 ℃ of hydrogen dividing potential drop: 0.8MPa | ?99.8 | 62.8 | 61.0 |
| Embodiment 10 | Pressure: 7.8MPa temperature: 280 ℃ of hydrogen dividing potential drop: 1.0MPa | ?99.8 | 63.0 | 61.5 |
| Embodiment 11 | Pressure: 7.9MPa temperature: 280 ℃ of hydrogen dividing potential drop: 0.9MPa | ?99.7 | 62.9 | 61.2 |
| Embodiment 12 | Pressure: 8.0MPa temperature: 280 ℃ of hydrogen dividing potential drop: 1.0MPa | ?99.9 | 63.2 | 62.0 |
Claims (6)
1. method that is used for the aromatic aldehyde selective hydrogenation of purification of terephthalic acid, in temperature of reaction is that 265～285 ℃, reaction pressure are 7.2～8.0MPa, the hydrogen dividing potential drop is under the condition of 0.5～1.5MPa, the terephthaldehyde's acid starting material that contains carboxyl benzaldehyde contacts with catalyzer, the reaction to carboxyl benzaldehyde in the raw material is generated hydroxymethyl-benzoic acid, and wherein used catalyzer comprises following component by weight percentage:
A) 0.05～1% palladium or its oxide compound;
B) 0.01～5% be selected from least a metal or its oxide compound in ruthenium, nickel, zinc, copper or the iron;
C) 94.0～99.8% carbon fibre carrier.
2. the aromatic aldehyde selective hydrogenation method that is used for purification of terephthalic acid according to claim 1 is characterized in that by weight percentage the consumption of palladium or its oxide compound is 0.1～0.8%.
3. the aromatic aldehyde selective hydrogenation method that is used for purification of terephthalic acid according to claim 1 is characterized in that by weight percentage, and being selected from least a metal in ruthenium, nickel, zinc, copper or the iron or the consumption of its oxide compound is 0.2～5%.
4. the aromatic aldehyde selective hydrogenation method that is used for purification of terephthalic acid according to claim 2 is characterized in that by weight percentage the consumption of palladium or its oxide compound is 0.2～0.5%.
5. the aromatic aldehyde selective hydrogenation method that is used for purification of terephthalic acid according to claim 3 is characterized in that by weight percentage, and being selected from least a metal in ruthenium, nickel, zinc, copper or the iron or the consumption of its oxide compound is 0.3～5%.
6. the aromatic aldehyde selective hydrogenation method that is used for purification of terephthalic acid according to claim 1 is characterized in that the carbon fibre carrier consumption is 95～99.8% by weight percentage.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112237913A (en) * | 2019-07-18 | 2021-01-19 | 中国石油化工股份有限公司 | Preparation method of palladium-based supported hydrogenation catalyst and catalyst thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1695805A (en) * | 2005-03-22 | 2005-11-16 | 华东理工大学 | Catalyst carried by Nano carbon fiber in use for refining terephthalic acid through hydrogen added |
| CN101347737A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst of aromatic aldehydes for refinement of terephthalic acid |
| CN101428226A (en) * | 2007-11-07 | 2009-05-13 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst for fine purification of p-benzene dicarboxylic acid |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1695805A (en) * | 2005-03-22 | 2005-11-16 | 华东理工大学 | Catalyst carried by Nano carbon fiber in use for refining terephthalic acid through hydrogen added |
| CN101347737A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst of aromatic aldehydes for refinement of terephthalic acid |
| CN101428226A (en) * | 2007-11-07 | 2009-05-13 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst for fine purification of p-benzene dicarboxylic acid |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112237913A (en) * | 2019-07-18 | 2021-01-19 | 中国石油化工股份有限公司 | Preparation method of palladium-based supported hydrogenation catalyst and catalyst thereof |
| CN112237913B (en) * | 2019-07-18 | 2024-05-03 | 中国石油化工股份有限公司 | Preparation method of palladium supported hydrogenation catalyst and catalyst thereof |
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